The present invention relates to a process for the controlled radical polymerization or copolymerization of ethylene under high pressure in the presence an initiator-controller.
The polymerization under high pressure of ethylene or its copolymerization under high pressure with comonomers which can copolymerize by the radical route results in a large variety of products which have numerous applications, among which may be mentioned bases for adhesives, in particular hot melt adhesives, bituminous binders, wrapping films, coextrusion binders, moulded items, and the like.
Processes for the polymerization of ethylene at high temperatures and pressures by means of free radical initiators have been known for a long time. Ethylene polymers are obtained by homopolymerizing ethylene or by copolymerizing it with at least one other comonomer in a polymerization system which operates continuously under pressures of the order of 50 MPa to 500 MPa and at temperatures of between 50 and 300xc2x0 C. The polymerization is carried out in continuous tubular reactors or stirred autoclaves in the presence of initiators and optionally of transfer agents. The polymers are subsequently separated from the volatile substances after their departure from the reactor in separators.
It is known that the polymerization of ethylene in the presence or in the absence of comonomers can result in reaction runaways (see, for example, Chem. Eng. Proc., 1998, 37, 55-59). These runaways are reflected by a very marked rise in the temperature and in the pressure and thus by bursting of the safety devices of the plant. Consequently, the runaway must result in undesired shutdowns in production. The aim is thus to avoid these shutdowns as far as possible and one means for doing this is to carefully control the flow rates of the reactants entering the reactor, in particular the flow rate of the source of radicals, that is to say of the initiator. This is because the injection of an excessively large amount of radicals results in a localized runaway in one of the regions of the reactor, which runaway subsequently spreads very quickly to the whole of the reactor. There thus exists a content of radicals not to be exceeded in order not to result in the runaway of the polymerization.
However, it is generally known that radical polymerizations can be controlled using stable free radicals, this control making it possible in particular to obtain polymers exhibiting narrow molecular mass distributions. Thus it is that United States Patent U.S. Pat. No. 5,449,724 discloses a radical polymerization process which consists in heating, at a temperature of approximately 40xc2x0 C. to approximately 500xc2x0 C. and under a pressure of approximately 50 MPa to 500 MPa, a mixture composed of a free radical initiator, of a stable free radical and of ethylene, in order to form a thermoplastic resin which has a molecular mass distribution of approximately 1.0 to approximately 2.0.
Furthermore, it is known, by International Patent Application WO 99/03894, to control the radical polymerization of monomers by the use, as (co)polymerization initiators, of specific alkoxyamines, these monomers being styrene, substituted styrenes, conjugated dienes, acrolein, vinyl acetate, anhydrides of (alkyl)acrylic acids, salts of (alkyl)acrylic acids, (alkyl)acrylic esters and alkyl-acrylamides. Ethylene is not mentioned as monomer. This polymerization is carried out under low pressure and at a temperature of between 50 and 180xc2x0 C., preferably between 80 and 150xc2x0 C., control of the reaction no longer being possible beyond 180xc2x0 C. In other words, such a process could not work for the (co)polymerization of ethylene under high pressure, in which (co)polymerization the temperature conditions generally exceed 1800xc2x0 C. This process furthermore exhibits the limitation according to which the polymers obtained have low molecular masses (not exceeding 15 000 in the examples).
In seeking to improve the known process for the controlled radical (co)polymerization of ethylene under high pressure, the Applicant Company has now discovered that, if use is made in (co)polymerization of an initiator-controller capable of providing at least one initiating free radical and at least one stable free radical, more specifically a free radical which is stable under the specific temperature conditions deployed in this high-pressure (co)polymerization, the latter is controlled under particularly favourable conditions while also controlling the reaction stability. The preferred initiators-controllers of the present invention, which will be described below, constitute a family of compounds which is not recommended according to WO 99/03894. It was therefore not obvious to thus control the high pressure (co)polymerization of ethylene, with greater effectiveness than with the use of an initiator and of a stable free radical, which are introduced separately, and with the observation, also surprising, that the (co)polymerization of ethylene takes place at a markedly greater rate. Furthermore, with the process of the invention, there is no limitation on the molecular masses of the (co)polymers obtained.
In addition, another consequence of the present invention is that, in the case where the initiator-controller chosen is such that it provides an initiating free macroradical, block copolymers are produced in which at least one of the blocks comprises ethylene as constituent. In point of fact, ethylene copolymers prepared under high pressure currently have random structures and it has not been possible to date to obtain such block copolymers having an ethylene-based block. It is well known that the structure of block copolymers can result in markedly better physicochemical properties than random copolymers. The present invention thus makes it possible to achieve the production of novel materials having novel properties.
The subject-matter of the present invention is thus first a process for the radical polymerization or copolymerization of ethylene under high pressure in the presence of at least one polymerization initiating-controlling compound capable of providing, by decomposition under the polymerization or copolymerization conditions:
at least one initiating free radical (Z) which carries at least one site for initiating the (co)polymerization; and
at least one stable free radical (SFR) which carries at least one site exhibiting the stable radical state and which is stable under the polymerization conditions,
with, in total, as many initiating sites as sites exhibiting the stable radical state.
In other words, when the initiator-controller dissociates, it produces, in the medium, as many initiating sites as stable radical sites. In the simplest case, the initiator-controller is such that it dissociates to give one initiating free radical and one stable free radical, the two radicals being monofunctional. Use may also be made of initiators-controllers which dissociate to give an n-functional initiating free radical and n monofunctional stable free radicals, or vice versa. Examples of various initiators-controllers are shown below.
The growing (co)polymer is thus positioned between the xe2x80x9cinitiatingxe2x80x9d part and the xe2x80x9ccontrollingxe2x80x9d part constituted by the stable free radical SFR.
The present invention thus involves the formation of a stable free radical. A stable free radical should not be confused with free radicals with a fleeting lifetime (a few milliseconds), such as the free radicals resulting from the usual polymerization initiators, such as peroxides, hydroperoxides and initiators of the azo type. The free radicals which initiate polymerization tend to accelerate the polymerization. In contrast, stable free radicals generally tend to slow down the polymerization. It may be generally said that a free radical is stable within the meaning of the present invention if it is not a polymerization initiator and if, under the operating conditions of the present invention, the mean lifetime of the radical is at least five minutes. During this mean lifetime, the molecules of the stable free radical continually alternate between the radical state and the state of a group bonded to a polymer chain via a covalent bond resulting from a coupling reaction between a radical centered on an oxygen atom and a radical centered on a carbon atom. Of course, it is preferable for the stable free radical to exhibit good stability throughout the duration of its use in the context of the present invention. Generally, a stable free radical can be isolated in the radical state at ambient temperature.
xe2x80x9cInitiating xe2x80x9d Part
In accordance with a first embodiment, the choice is made, as initiating-controlling compound, of a compound capable of providing at least one monofunctional radical Z chosen from those of the formulae (Ia) or (Ib) or (Ic): 
in which:
R1, R2, R3, R4, R5, R6 and R7 each independently represent:
optionally substituted C1-24 alkyl;
optionally substituted C1-24 aryl;
it also being possible for R1, R2, R3, R4, R5 and R6 to each independently denote a hydrogen atom.
As examples of this first embodiment, the choice is made, as initiating-controlling compound, of a compound capable of providing at least one monofunctional radical Z chosen from those of the formulae (Ia1), (Ia2) or (Ia3): 
with n=0 or an integer from 1 to 23; 
with R8 representing hydrogen, methyl or ethyl; and 
with:
R9, R10, R11, R12 and R13 each independently representing alkyl, aryl or halogen; and
R14 representing alkyl or aryl.
In accordance with a second embodiment, the choice is made, as initiating-controlling compound, of a compound capable of providing a radical Z of formula (II):
Z1xe2x80x94(PM)1xe2x80x94[(PM)2]xe2x80xa2xe2x80x83xe2x80x83(II)
in which:
Z1 represents the initiating fragment of a radical initiator;
(PM)1 represents a polymer block formed by living radical polymerization or copolymerization of at least one monomer which can polymerize by the radical route in the presence of an initiator which produces free radicals Z1xe2x80xa2; and
(PM)2, the presence of which is optional, represents another polymer block, other than (PM)1, formed by living radical polymerization or copolymerization of at least one monomer which can polymerize by the radical route in the presence of the initiator Z1-(PM)1xe2x80xa2.
Mention may be made, as examples of (PM)1 and (PM)2 blocks, of those of the formulae: 
where:
T and U each independently represent hydrogen or a substituted or unsubstituted C1-10 alkyl residue;
V and W each independently represent hydrogen, substituted or unsubstituted alkyl, substituted or unsubstituted aryl, xe2x80x94COOH, xe2x80x94COOR15, xe2x80x94CN, xe2x80x94CONH2, xe2x80x94CONHR16, xe2x80x94CONR17R18, 
or xe2x80x94OR20, R15 to R20 each independently representing substituted or unsubstituted alkyl or substituted or unsubstituted aryl; and
n denotes the degree of polymerization, which can in particular range up to 10 000.
This second embodiment thus relates to the use of macroinitiators-controllers, the xe2x80x9cmacro-initiatorxe2x80x9d part of which is prepared in a known way by living radical (co)polymerization under high pressure (for example greater than 100 MPa), in the case where ethylene participates in the preparation of at least one of the blocks (T=U=V=W=H), or under low pressure, in the contrary case.
In accordance with a third embodiment, the choice is made, as initiating-controlling compound, of a compound capable of providing a polyfunctional radical Z carrying a plurality of initiating sites of 
type. The functionality can vary between 2 and 10, preferably being between 2 and 4.
Mention may be made, by way of example, of a compound capable of providing a polyfunctional radical Z of formula: 
xe2x80x9cControllingxe2x80x9d Part
The choice is advantageously made, as initiating-controlling compound, of a compound capable of providing at least one nitroxyl stable free radical comprising at least onexe2x95x90Nxe2x80x94Oxe2x80xa2 group.
The stable free radical or radicals is/are chosen in particular from nitroxide radicals, that is to say comprising thexe2x95x90Nxe2x80x94Oxe2x80xa2 group, in particular from those of the formulae (IIIa), (IIIb) or (IIIc): 
in which:
Rxe2x80x21 to Rxe2x80x23, Rxe2x80x25 to Rxe2x80x28 and Rxe2x80x213 and Rxe2x80x214 each independently represent:
(a) a hydrogen atom;
(b) a halogen atom, such as chlorine, bromine or iodine;
(c) a saturated or unsaturated and linear, branched or mono- or polycyclic hydro-carbonaceous group which can be substituted by at least one halogen;
(d) an ester group xe2x80x94COORxe2x80x215 or an alkoxyl group xe2x80x94ORxe2x80x216, Rxe2x80x215 and Rxe2x80x216 representing a hydrocarbonaceous group as defined in point (c) above;
(e) a polymer chain which can, for example, be a poly(alkyl methacrylate) or poly(alkyl acrylate) chain, such as poly(methyl methacrylate), a polydiene chain, such as polybutadiene, or a polyolefin chain, such as polyethylene or polybutadiene but preferably being a polystyrene chain;
Rxe2x80x24 has the meanings defined in points (a), (b), (c), (d) and (e) above;
Rxe2x80x29 to Rxe2x80x212, which are identical or different, have the meanings defined in points (a) to (e) above and can in addition represent a hydroxyl group or an acid group, such as xe2x80x94COOH or xe2x80x94SO3H;
it being possible for Rxe2x80x23 and Rxe2x80x24 to be connected to one another and, in the case where Rxe2x80x24 represents a xe2x80x94CRxe2x80x31Rxe2x80x32Rxe2x80x33 residue (Rxe2x80x31 to Rxe2x80x33 having without distinction the meanings of Rxe2x80x21 to Rxe2x80x23), it being possible for Rxe2x80x23 to be connected to Rxe2x80x33, to form a heterocycle comprising the nitrogen atom of 
it being possible for the said heterocycle to be saturated or unsaturated, to comprise, in the ring, at least one other heteroatom and/or at least one 
group and also to comprise a saturated or unsaturated fused ring;
it being possible for two from Rxe2x80x21 to Rxe2x80x23, Rxe2x80x25 and Rxe2x80x26, Rxe2x80x27 and Rxe2x80x28, Rxe2x80x29 and Rxe2x80x210, Rxe2x80x211 and Rxe2x80x212, Rxe2x80x26 and Rxe2x80x29, Rxe2x80x28 and Rxe2x80x211, Rxe2x80x213 and Rxe2x80x214 and, in the case where Rxe2x80x24 represents a xe2x80x94CRxe2x80x31Rxe2x80x32Rxe2x80x33 residue, Rxe2x80x23 and Rxe2x80x33 independently to be connected to one another to form, with the carbon atom which carries them, a saturated or unsaturated ring or heterocycle;
u is a non zero integer, for example from 1 to 18.
Mention may be made, as examples of hydrocarbonaceous groups as defined in point (c) above, of those having from 1 to 20 carbon atoms, such as linear, branched or cyclic alkyl radicals and aryl radicals, for example phenyl or naphthyl, and radicals comprising at least one aromatic ring which can be substituted, for example by a C1-C4 alkyl radical, such as aralkyl radicals, for example benzyl.
Mention may in particular be made of nitroxide radicals comprising a sequence,of formula: 
in which the RL radical exhibits a molar mass of greater than 15. The monovalent RL radical is said to be in the xcex2-position with respect to the nitrogen atom of the nitroxide radical. The remaining valences of the carbon atom and of the nitrogen atom in the formula (1) can be bonded to various radicals, such as a hydrogen atom or a hydrocarbonaceous radical, such as an alkyl, aryl, or aralkyl radical, comprising from 1 to 10 carbon atoms. It is not excluded that the carbon atom and the nitrogen atom in the formula (1) should be connected to one another via a bivalent radical, so as to form a ring. However, the remaining valences of the carbon atom and of the nitrogen atom of the formula (1) are preferably bonded to monovalent radicals. The RL radical preferably exhibits a molar mass of greater than 30. The RL radical can, for example, have a molar mass of between 40 and 450. The RL radical can also comprise at least one aromatic ring, as for the phenyl radical or the naphthyl radical, it being possible for the latter to be substituted, for example by an alkyl radical comprising from 1 to 4 carbon atoms.
A specific family of nitroxide radicals which can be envisaged in accordance with the present invention is that of the nitroxide radicals of formula (IIIa) in which Rxe2x80x23 and Rxe2x80x24 (or Rxe2x80x23 and Rxe2x80x33) are connected to one another and which are chosen in particular from: 
where:
Ra to Rk and Rm independently have the meanings given for Rxe2x80x29 to Rxe2x80x212, it being possible for Ra and Rb and Re and Rf to be identical or different when they are carried by different carbon atoms;
r has the value 2 or 3 or 4;
s a non zero integer, in particular from 1 to 10;
t has the value 0, 1 or 2.
The following may furthermore be indicated, as specific examples of nitroxide radicals:
2,2,5,5-tetramethyl-1-pyrrolidinyloxy (generally sold under the trade name PROXYL): 
3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (commonly known as 3-carboxy-PROXYL);
2,2,6,6-tetramethyl-1-piperidinyloxy (commonly known as TEMPO): 
4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (commonly known as 4-hydroxy-TEMPO);
4-methoxy-2,2,6,6-tetramethyl-1-piperidinyloxy (commonly known as 4-methoxy-TEMPO):
4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy (commonly known as 4-oxo-TEMPO);
bis(1-oxyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, represented by the formula: 
(sold under the trade name xe2x80x9cCXA 5415xe2x80x9d by xe2x80x9cCiba Specialty Chemicalxe2x80x9d);
N-tert-butyl-1-phenyl-2-methylpropyl nitroxide: 
N-tert-butyl-1-(2-naphthyl)-2-methylpropyl nitroxide.
In a particularly preferred way, however, use is made of an alkoxyamine as initiating-controlling compound and more particularly of an alkoxyamine for which the nitrogen atom of the nitroxide group forms part of a C5-12 ring, the other atoms of which are generally carbon atoms.
Mention may also particularly be made of alkoxyamines, the nitroxide of which does not decompose to more than 50% over 2 hours at 180xc2x0 C. under 200 MPa (2 000 bar) in heptane.
The alkoxyamines are known compounds or compounds the manufacture of which has been described in the literature. Reference may be made, inter alia, to Macromolecules, 1996, 29, 5245-5254, to Macromolecules, 1996, 29, 7661-7670, and to French Patent Application No. 99-04405 of 8 Apr. 1999 on behalf of the Applicant Company.
Specific examples of initiators-controllers of the present invention are the following: 
(2,2,6,6-tetramethyl-1-piperidinyloxyhexane) 
In accordance with the present invention, the ratio of the initiating-controlling compound/monomer(s) is generally within the range from 0.0001% to 10% by weight, in particular within the range from 0.0005% to 5% by weight.
Furthermore, the (co)polymerization of the present invention is generally carried out under a pressure of 150 to 300 MPa, in particular of 150 to 250 MPa, and at a temperature of 100 to 300xc2x0 C., in particular of 180 to 250xc2x0 C.
There is no limitation with regard to the molecular masses of the (co)polymers obtained according to the invention. According to the polymerization or copolymerization conditions and in particular the duration, the temperature or the degree of conversion of monomer to polymer or copolymer, it is possible to prepare products of different molecular masses. In particular, in the case of the polymerization of ethylene, the process of the invention is carried out at a temperature, a pressure and a duration which are sufficient for the polyethylene obtained to have a weight-average molecular mass of greater than 80 000 and a number-average molecular mass of greater than 20 000.
The process according to the invention can be carried out in the presence of a solvent. The solvent is chosen in particular from benzene, toluene, xylene, ethyl acetate, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, amyl alcohol, dimethyl sulphoxide, glycol, dimethylformamide, tetrahydrofuran and their mixtures, the solvent/polymerization ingredients (namely monomer(s)+initiator-controller) ratio by weight advantageously being at most 5.
The process according to the present invention can also be carried out in the presence of a transfer agent in the usual amounts. The transfer agents which can be used are well known to a person skilled in the art who is an expert in the (co)polymerization of ethylene under high pressure. Mention may in particular be made of alkanes, for example butane, alkenes, for example propylene, and oxygen-comprising derivatives, such as, for example, aldehydes or alcohols.
In accordance with the present invention, the ethylene can be copolymerized with any other monomer exhibiting a carbon-carbon double bond capable of polymerizing or copolymerizing by the radical route.
The monomer or monomers can thus be chosen from vinyl, allyl, vinylidene, diene and olefinic monomers (other than ethylene).
The term xe2x80x9cvinyl monomersxe2x80x9d is understood to mean in particular (meth)acrylates, vinylaromatic monomers, vinyl esters, vinyl ethers, (meth)acrylonitrile, (meth)acrylamide and mono- and di(C1-C18 alkyl) (meth)acrylamides, and monoesters and diesters of maleic anhydride and of maleic acid.
The (meth)acrylates are in particular those of the formulae respectively: 
in which R0 is chosen from C1-C18 alkyl radicals of linear or branched and primary, secondary or tertiary type, C5-C18 cycloalkyl radicals, (C1-C18)alkoxy(C1-C18)-alkyl radicals, (C1-C18)alkylthio(C1-C18)alkyl radicals, aryl radicals and arylalkyl radicals, these radicals optionally being substituted by at least one halogen atom and/or at least one hydroxyl group, the above alkyl groups being linear or branched; and glycidyl, norbornyl or isobornyl (meth)acrylates.
Mention may be made, as examples of useful methacrylates, of methyl, ethyl, 2,2,2-trifluoroethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-amyl, i-amyl, n-hexyl, 2-ethylhexyl, cyclohexyl, octyl, i-octyl, nonyl, decyl, lauryl, stearyl, phenyl, benzyl, xcex2-hydroxyethyl, isobornyl, hydroxypropyl or hydroxybutyl methacrylates. Mention may be made, in particular, of methyl methacrylate.
Mention may be made, as examples of acrylates of the above formula, of methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, hexyl, 2-ethylhexyl, isooctyl, 3,3,5-trimethylhexyl, nonyl, isodecyl, lauryl, octadecyl, cyclohexyl, phenyl, methoxymethyl, methoxyethyl, ethoxymethyl and ethoxyethyl acrylates.
The term xe2x80x9cvinylaromatic monomerxe2x80x9d is understood to mean, within the meaning of the present invention, an aromatic monomer comprising ethylenic unsaturation, such as styrene, vinyltoluene, xcex1-methylstyrene, 4-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-(hydroxymethyl)styrene, 4-ethylstyrene, 4-ethoxystyrene, 3,4-dimethylstyrene, styrenes substituted on the ring by a halogen, such as 2-chlorostyrene, 3-chlorostyrene, 4-chloro-3-methylstyrene, 4-chloro-3-(tert-butyl)styrene, 2,4-dichlorostyrene and 2,6-dichlorostyrene, 1-vinylnaphthalene and vinylanthracene.
Mention may be made, as vinyl esters, of vinyl acetate, vinyl propionate, vinyl chloride and vinyl fluoride and mention may be made, as vinyl ethers, of vinyl methyl ether and vinyl ethyl ether.
Mention is made, as vinylidene monomer, of vinylidene fluoride.
The term xe2x80x9cdiene monomerxe2x80x9d is understood to mean a diene chosen from conjugated or nonconjugated and linear or cyclic dienes, such as, for example, butadiene, 2,3-dimethylbutadiene, isoprene, chloroprene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,9-decadiene, 5-methylene-2-norbornene, 5-vinyl-2-norbornene, 2-alkyl-2,5-norbornadienes, 5-ethylene-2-norbornene, 5-(2-propenyl)-2-norbornene, 5-(5-hexenyl)-2norbornene, 1,5-cyclooctadiene, bicyclo[2.2.2]octa-2,5-diene, cyclopentadiene, 4,7,8,9-tetrahydroindene, isopropylidenetetrahydroindene and piperylene.
Mention may be made, as olefinic monomers, of olefins comprising from three to twenty carbon atoms and in particular the a-olefins of this group. Mention may be made, as olefin, of propylene, 1-butene, 4-methyl-1-pentene, 1-octene, 1-hexene, isobutylene, 3-methyl-1-pentene, 3-methyl-1-butene, 1-decene, 1-tetradecene or their mixtures. Fluorinated olefinic monomers may also be mentioned.
Mention may also be made, as (co)polymerizable monomers, of xcex1- or xcex2-ethylenically unsaturated C3-8 carboxylic acids, such as maleic acid, fumaric acid, itaconic acid, acrylic acid, methacrylic acid and crotonic acid; or xcex1- or xcex2-ethylenically unsaturated carboxylic acid anhydrides, such as maleic anhydride or itaconic anhydride.
Preferred comonomers are, inter alia, vinyl acetate, n-butyl acrylate, 2-ethylhexyl acrylate, methyl acrylate and ethyl acrylate.
The process according to the invention is carried out in a tubular reactor or autoclave or a combination of the two.
Autoclave and tubular processes are both included among the polymerization processes referred to as xe2x80x9chigh pressurexe2x80x9d polymerization processes known to a person skilled in the art. These two processes involve the polymerization of ethylene by the radical route under high pressure, generally between 100 and 350 MPa, and at temperatures greater than the melting temperature of the polyethylene being formed. The tubular process involves polymerization in a tubular reactor. A tubular reactor comprises cylinders with an internal diameter generally of between 1 and 10 cm and a length generally ranging from 0.1 to 3 km. In a tubular reactor, the reaction mixture is driven with a high linear speed, generally of greater than 2 metres per second, with short reaction times which can, for example, be between 0.1 and 5 min.
The pressure in the tubular reactor can, for example, be between 200 and 350 MPa, preferably between 210 to 280 MPa, for example between 230 and 250 MPa. The temperature in the tubular reactor can range from 120 to 350xc2x0 C. and preferably from 150 to 300xc2x0 C.
The autoclave process involves polymerization 20 in an autoclave with a length/diameter ratio generally ranging from 1 to 25, in the case of a single-zone reactor. In the case of a multiple-zone reactor, the length of each zone/diameter ratio generally ranges from 0.5 to 6, it being understood that the reaction mixture flows in the lengthwise direction.
The pressure in the autoclave reactor can, for example, be between 100 and 250 MPa, preferably between 120 and 180 MPa, for example between 140 and 170 MPa. The temperature in the autoclave reactor can range from 180 to 300xc2x0 C., preferably from 240 to 290xc2x0 C.
The present invention also relates to block copolymers for which at least one of the blocks comprises ethylene as constituent. As already indicated above, these block copolymers are prepared by using the macroinitiators-controllers described above with reference to the second embodiment.
Mention may in particular be made of the block copolymers of the type:
Polystyrene-(b) -polyethylene
Polyacrylate-(b)-polyethylene
Polymethacrylate-(b)-polyethylene
Poly(styrene-(co)-acrylate)-(b)-polyethylene
Polystyrene-(b)-poly(ethylene-(co)-acrylate)
Polystyrene-(b)-poly(ethylene-(co)-vinyl acetate),
it being possible for such block copolymers, as well as the homopolymers of ethylene and the random copolymers obtained according to the invention, to have numerous applications as base for adhesives, for coextrusion binders, for films, for bituminous binders, for packaging, for moulded items, and the like.